Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
  • C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups

Definitions

• the present invention relates to novel triazine derivatives and the use thereof to stabilize a broad range of substrates against light-induced degradation.
• sterically hindered amines include various (tetraalkyl-4-piperidyl)amino-triazine derivatives.
• Reference is made to U.S. 3,925,376, U.S. 4,086,204, U.S. 4,108,829, U.S. 4,477,615, U.S. 4,533,688 and U.S. 4,547,548 are representative disclosures in this area.
• These hindered amine light stabilizers do not possess structures having an O-substituted moiety substituted directly on the nitrogen atom of the hindered amine.
• N-unsubstituted and N-alkyl substituted 2,2,6,6-tetramethylpiperidin-4-yloxy-­ 1,3,5-triazines are noted in U.S. 4,314,933 and U.S. 4,426,471.
• N-alkoxy (C1-C12)-2,2,6,6-tetra­methylpiperidin-4-yl derivatives of 1,3,5-triazine are generically claimed in U.S. 4,740,544.
• R is hydrogen or methyl
• R1 is C1-C18-alkyl, C2-C18-alkenyl, C2-C18-alkynyl, C5-C12-cycloalkyl, C5-C12-cycloalkenyl, C6-C10-bicycloalkyl, C6-C10-aryl, C7-C12-aralkyl or C7-C12-aralkyl substituted by C1-C12-alkyl or C6-C10-aryl;
• R2 is hydrogen, C1-C12-alkyl or Y is a direct bond or m, p and q are independently 2-6;
• A is oxygen, sulfur or -N(R2)-;
• n is 2-4; and
• R3 is an n-valent alkane or aryl radical.
• Alkyl groups are preferably C1-C12 and include methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, decyl, dodecyl as well as octadecyl.
• Cycloalkyl is preferably cyclopentyl and cyclohexyl.
• Alkenyl is preferably vinyl and allyl while alkynyl is preferably propargyl.
• Aryl is preferably phenyl, naphthyl and tolyl while aralkyl is preferably benzyl, alpha-methylbenzyl and alpha,alpha-dimethylbenzyl.
• R1 is most preferably methyl, heptyl, octyl and cyclohexyl.
• R2 is most preferably hydrogen or C1-C4-alkyl and particularly hydrogen or n-butyl.
• m, p and q are preferably 2, 3 or 6 with Y being either the direct bond or the substituted triazine.
• A is preferably oxygen or -N(R2)- with the above identified R2 preferences.
• R3 is preferably straight chain or branched C1-C12-­alkylene including methylene, ethylene and hexamethylene, C2-C6-alkylidene, C5-C10-cycloalkylene, C6-C10-arylene including phenylene, xylylene and naphthylene, or alkylenearylenealkylene of 8 to 10 carbon atoms.
• a as oxygen with R3 as p-phenylene and A as -NH- with R3 as ethylene or hexamethylene are particularly preferred.
• R3 is preferably alkanetriyl of 3 to 6 carbon atoms such as glyceryl or trimethylylpropane, or aryl-triyl of 6 to 10 carbon atoms.
• R3 is preferably alkanetetrayl of 4 to 6 carbon atoms such as pentaerythrityl or aryl-tetrayl of 6 to 10 carbon atoms.
• Trivalent and tetravalent groups also include
• the compounds of the invention can be prepared by reacting cyanuric chloride or derivatives of cyanuric chloride with 4-hydroxy-1-hydrocarbyloxy-2,2,6,6-tetraalkyl­piperidines in the presence of an inert solvent such as acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, xylene, and the like, and in the presence of a strong base such as sodium hydride.
• an inert solvent such as acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, xylene, and the like
• U.S. Patent No. 4,665,185 teaches the preparation of N-hydroxypiperidines by oxidation of the hindered amine with an appropriate peroxy compound such as hydrogen peroxide and a metal oxide catalyst followed by catalytic hydrogenation.
• the N-hydroxy compounds can be alkylated by reaction with sodium hydride and halogenated hydrocarbons.
• the preferred method of making the N-hydrocarbyl compounds involves the thermal reaction of a hydrocarbon solution, especially effective with hydrocarbons such as cyclohexane, heptane, octane, nonane or ethylbenzene, of the hindered amine or its N-oxyl derivative with tert-butyl hydroperoxide and a metal oxide catalyst. See EP-A-309 402.
• the starting materials needed to prepare these compounds are items of commerce or can be prepared by known methods.
• the invention also relates to compounds wherein the following tetraalkyl substituted piperazine or piperazinone moieties are substituted for the above-noted tetraalkylpiperidine moiety: wherein M and Y are independently methylene or carbonyl, preferably M being methylene and Y being carbonyl. It is understood that the identified substituents applicable to such compounds are those which are appropriate for substitution on the ring nitrogen atoms.
• Substrates in which the compounds of this invention are particularly useful are polyolefins such as poly­ethylene and polypropylene; polystyrene, including especially impact polystyrene; ABS resin; elastomers such as e.g. butadiene rubber, EPM, EPDM, SBR and nitrile rubber.
• polymers which can be stabilized include
• the stabilizers of this invention are employed in from about 0.01 to about 5% by weight of the stabilized composition, although this will vary with the particular substrate and application.
• An advantageous range is from about 0.5 to about 2%, and especially 0.1 to about 1%.
• the stabilizers of the instant invention may readily be incorporated into the organic polymers by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom.
• the stabilizer may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer.
• the stabilized polymer compositions of the invention may optionally also contain various conventional additives, such as the following.
• the present invention also relates to the use of the instant compounds, optionally together with further stabilizers, for stabilizing ambient cured coatings based on alkyd resins; thermoplastic acrylic resins; acrylic alkyds; acrylic alkyd or polyester resins optionally modified with silicon, isocyanates, isocyanurates, ketimines or oxazolidines; and epoxide resins crosslinked with carboxylic acids, anhydrides, polyamines or mercaptans; and acrylic and polyester resin systems modified with reactive groups in the backbone thereof and crosslinked with epoxides; against the degradative effects of light, moisture and oxygen.
• enamels with high solids content based on crosslinkable acrylic, polyester, urethane or alkyd resins are cured with an additional acid catalyst.
• Light stabilizers containing a basic nitrogen group are generally less than satisfactory in this application. Formation of a salt between the acid catalyst and the light stabilizer leads to incompatibility or insolubility and precipitation of the salt and to a reduced level of cure and to reduced light protective action and poor resistance to moisture.
• acrylic resin lacquers which can be stabilized against light, moisture and oxygen in accordance with the invention, are the conventional acrylic resin stoving lacquers or thermosetting resins including acrylic/melamine systems which are described, for example, in H. Kittel's "Lehrbuch der Lacke und Be harshungen", Vol. 1 Par 2, on pages 735 and 742 (Berlin 1972), “Lackkunstharze” (1977), by H. Wagner and H.F. Sarx, on pages 229-238, and in S. Paul's "Surface Coatings: Science and Technology” (1985).
• polyester lacquers which can be stabilized against the action of light and moisture, are the conventional stoving lacquers described e.g. in H. Wagner and H.F. Sarx, op. cit., on pages 86-99.
• the alkyd resin lacquers which can be stabilized against the action of light and moisture in accordance with the invention are the conventional stoving lacquers which are used in particular for coating automobiles (automobile finishing lacquers), for example lacquers based on alkyd/­melamine resins and alkyd/acrylic/melamine resins (see H. Wagner and H. F. Sarx, op. cit., pages 99-123).
• Other crosslinking agents include glycoluril resins, blocked isocyanates or epoxy resins.
• the acid catalyzed stoving lacquers stabilized in accordance with the invention are suitable both for metal finish coatings and solid shade finishes, especially in the case of retouching finishes, as well as various coil coating applications.
• the lacquers stabilized in accordance with the invention are preferably applied in the conventional manner by two methods, either by the single-­coat method or by the two-coat method. In the latter method, the pigment-containing base coat is applied first and then a covering coat of clear lacquer over it.
• the instant substituted hindered amines are applicable for use in non-acid catalyzed thermoset resins such as epoxy, epoxy-polyester, vinyl, alkyd, acrylic and polyester resins, optionally modified with silicon, isocyanates or isocyanurates.
• the epoxy and epoxy-polyester resins are crosslinked with conventional crosslinkers such as acids, acid anhydrides, amines, and the like.
• the epoxide may be utilized as the crosslinking agent for various acrylic or polyester resin systems that have been modified by the presence of reactive groups on the backbone structure.
• these additional light stabilizers can be added to the clear coat and/or the pigmented base coat.
• the sum of all light stabilizers is 0.2 to 20% by weight, preferably 0.5 to 5% by weight, based on the film-forming resin.
• UV absorbers examples include the phenyl salicylates, the o-hydroxybenzophenones, the hydroxyxanthones, the benzoxazoles, the benzimidazoles, the oxadiazoles, the triazoles, the pyrimidines, the chinazolines, the s-triazines, the hydroxyphenyl-benzotria­zoles, the alpha-cyanoacrylates and the benzoates.
• UV absorbers of especial importance are:
• benzotriazoles of high molecular weight and low volatility such as 2-[2-hydroxy-3,5-di(alpha,alpha-di­methylbenzyl)-phenyl]-2H-benzotriazole, 2-(2-hydroxy-3,5-­di-tert-octylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-­alpha,alpha-dimethylbenzyl-5-tert-octyl-phenyl)-2H-benzo­triazole, 2-(2-hydroxy-3-tert-octyl-5-alpha,alpha-dimethyl­benzylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert-­amylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-­(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl)-ethyl
• benzotriazoles useful in the instant compositions are 2-[2-hydroxy-3,5-di(alpha,alpha-­dimethyl-benzyl)phenyl]-2H-benzotriazole, dodecylated 2-(2-­hydroxy-5-methylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3-­tert-butyl-5-(2-(omega-hydroxy-octa-(ethyleneoxy) carbonyl)-ethylphenyl]-2H-benzotriazole, 2-[2-hydroxy-3-­tert-butyl-5-(2-octyloxycarbonyl)ethylphenyl]-2H-benzotri­azole and 5-chloro-2-[2-hydroxy-3-tert-butyl-5-(2-octyl­oxycarbonyl)ethylphenyl]-2H-benzotriazole.
• the instant compounds will be particularly effective as stabilizers for polyolefin fibers, especially polypropylene fibers, when used in conjunction with other stabilizers selected from the group consisting of the phenolic antioxidants, hindered amine light stabilizers, organic phosphorus compounds, ultraviolet absorbers and mixtures thereof.
• antioxidants for example those of the sterically hindered phenol derivatives, phosphorus compounds, such as phosphites, phosphines or phosphonites, plasticizers, levelling assistants, hardening catalysts, thickeners, dispersants or adhesion promoters.
• a further preferred embodiment of the instant invention is a stabilized composition containing components (a), (b) and (c) described above which additionally contains as component (d) a phosphite or phosphonite.
• the amount of phosphite or phosphonite (d) which is used in the instant compositions is from 0.05 to 2% by weight, preferably from 0.1 to 1% by weight, based on the film forming resin. In two-coat systems, these stabilizers may be added to the clear coat and/or base coat.
• Typical phosphite and phosphonites include triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl)phosphite, trilauryl phosphite trioctadecyl phosphite, di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert.butylphenyl) phosphite, di­isodecylpentaerythritol diphosphite, di-(2,4-di-tert.butyl­phenyl)pentaerythritol diphosphite, tristearyl-sorbitol triphosphite, tetrakis-(2,4-di-tert.butylphenyl)-4,4′-di­phenylylenediphosphonite.
• the acid catalyzed thermoset enamels must be stabilized in order to function acceptably in end-use applications.
• the stabilizers used are hindered amines, preferably those substituted on the N-atom by an inert blocking group in order to prevent precipitation of the basic amine stabilized with the acid catalyst with a concomitant retardation in cure, optionally in combination with UV absorbers, such as the benzotriazoles, benzophenones, substituted s-triazines, phenyl benzoates or oxanilides.
• the stabilizers are needed to impart greater retention of durability to the cured enamels (as measured by 20° gloss, distinction of image, cracking or chalking); the stabilizers must not retard cure (normal bake for auto finishes at 121°C and low bake repair at 82°C (as measured by hardness, adhesion, solvent resistance and humidity resistance), the enamel should not yellow on curing and further color change on exposure to light should be minimized; the stabilizers should be soluble in the organic solvents normally used in coating applications such as methyl amyl ketone, xylene, n-hexyl acetate, alcohol and the like.
• the instant hindered amine light stabilizers substituted on the N-atom by an O-substituted moiety fulfill each of these requirements and provide alone or in combination with a UV-absorber outstanding light stabilization protection to the cured acid catalyzed thermoset enamels.
• Still another preferred combination of the instant stabilizers is with a hydroxylamine in order to protect polypropylene fibers from gas fading.
• Salts are removed by filtration, and the salt cake is slurried in water and filtered to remove salt from the product, a solid.
• the crude product is dissolved in boiling methanol and residual salt is removed by filtration. Additional product is recovered from the dioxane filtration. Crude solids are combined and heated in refluxing 2-propanol. Th resulting suspension is allowed to cool, and the solid is isolated by filtration to afford 19.4 g (59% yield) of the title compound, a white solid, m.p. 242-5°C (dec.).
• the title compound is prepared by the reaction of 4-hydroxy-1-methoxy-2,2,6,6-tetramethylpiperidine, sodium hydride, and cyanuric chloride in 1,4-dioxane solvent.
• the title compound is prepared by the reaction of 4-hydroxy-1-octyloxy-2,2,6,6-tetramethylpiperidine, sodium hydride, and cyanuric chloride in 1,4-dioxane solvent.
• a mixture of 22.6 g (88.6 mmol) of 1-cyclohexyloxy-4-­hydroxy-2,2,6,6-tetramethylpiperidine, 2.13 g (88.6 mmol) of sodium hydride, and 150 ml of 1,4-dioxane is heated at reflux for 2.5 hours.
• the reaction mixture is cooled to 60°C and treated with a solution of 7.8 g (17.7 mmol) of N,N′-dimethyl-N,N′-bis(2,4-dichloro-1,3,5-triazin-6-yl)-1,6-­hexanediamine in 50 ml of dioxane.
• the reaction mixture is quenched with ice.
• the title compound is prepared by substituting 1,2-bis[(2,4- dichloro-1,3,5-triazin-6-yl)thio]ethane for N,N′-dimethyl-N,N′-bis(2,4-dichloro-1,3,5-triazin-6-yl)-­1,6-hexanediamine in Example 4.
• this invention is seen to provide a series of new hindered-amine substituted triazine derivatives. Variations may be made in proportions, procedures and materials without departing from the scope of the invention as defined by the following claims.
• thermoset acrylic enamel based on a binder of 70% by weight of 2-hydroxyethyl acrylate, butyl acrylate, methyl methacrylate, styrene and acrylic acid and of 30% by weight of a melamine resin in the presence of an acid catalyst, p-toluenesulfonic acid, dinonylnaphthalene disulfonic acid or dodecylbenzenesulfonic acid, is formulated to include 2% by weight based on the resin solids of a benzotriazole ultraviolet absorber and an effective stabilizing amount of the test hindered amine light stabilizer.
• the coated panels are subjected to weathering in a QUV exposure apparatus according to test method ASTM G-53/77.
• ASTM G-53/77 the samples are subjected to weathering in repeated cycles for 4 hours in a humid atmosphere at 50°C and then for 8 hours under UV light at 70°C.
• the panels are exposed in the QUV for 1500 hours.
• the 20° gloss values of the panels are determined before and after exposure.
• the loss of gloss of the stabilized panels is considerably less than that of the unstabilized control panels.
• This example illustrates the light stabilizing effectiveness of instant stabilizers.
• Polypropylene powder (Himont Profax 6501) stabilized with 0.2% by weight of n-octadecyl 3,5-di-tert-butyl-4-­hydroxyhydrocinnamate is thoroughly blended with the indicated amount of additive.
• the blended materials are then milled on a two-roll mill at 182°C for five minutes, after which time the stabilized polypropylene is sheeted from the mill and allowed to cool.
• the milled polypropylene is then cut into pieces and compression molded on a hydraulic press at 250°C and 175 psi (1.2 x 106 Pa) into 5 mil (0.127 mm) films.
• the sample is exposed in a fluorescent sunlight/black light chamber until failure. Failure is taken as the hours required to reach 0.5 carbonyl absorbance by infrared spectroscopy on the exposed films.
• the time to failure for a polypropylene composition containing an instant compound as stabilizer is far longer than the time to failure for polypropylene having no such stabilizer present.

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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Plural Heterocyclic Compounds (AREA)

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• 1990
  • 1990-03-13 EP EP19900810199 patent/EP0389431B1/de not_active Expired - Lifetime
  • 1990-03-13 DE DE1990608406 patent/DE69008406T2/de not_active Expired - Fee Related
  • 1990-03-19 CA CA 2012500 patent/CA2012500C/en not_active Expired - Fee Related
  • 1990-03-21 BR BR9001307A patent/BR9001307A/pt not_active IP Right Cessation
  • 1990-03-22 JP JP2073182A patent/JP2879160B2/ja not_active Expired - Lifetime

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